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By Roy J. M. van Lier

In industrial aqueous solutions, germanium generally occurs in trace amounts amid high concentrations of other metals, such as zinc, copper and iron. Separation of germanium from these metals as well as its isolation from gallium and indium pose a real challenge to the hydrometallurgist. After a brief discussion of the aqueous chemistry of germanium, this paper reviews the flowsheet of the Apex Mine in Utah. The Apex property was the only mine in the world to be operated primarily for production of gallium and germanium, but apparently closed due to great operating difficulties. Several process variants proposed for the treatment of the Apex ore, including bioleaching methods, are addressed. Following a more general description of the behavior of germanium in hydrometallurgical zinc processing streams, available technology for its recovery from aqueous solutions is summarized. Precipitation, solvent extraction, ion exchange, electrowinning, ion flotation and liquid-membrane separation are all outlined in terms of the aqueous chemistry of germanium. Finally, the production of high purity germanium dioxide and metal is briefly discussed

Jan 1, 1995

By Abbas H. Mirza

Arsenic and selenium are found in low quantities together with other metals in several nonferrous metallurgical process streams such as scrubber blowdown solution, acid plant wastewater, gas cleaning plant water, etc. Normally, the other metals in these streams are present as cations and can be precipitated by conventional lime treatment and sulfide polishing. However, arsenic and selenium are invariably present as anions, AsO33-and AsO43 in the case of arsenic and SeO32 and SeO42 for selenium. Conventional lime treatment removes most of the arsenic, but it does not remove selenium. The present paper reviews the processes and technologies developed to date on the removal of arsenic and selenium from metallurgical process streams.

Jan 1, 1996

By R. W. Bartlett

The extensive central Idaho black sand placer deposits are a potential source of rare earth elements, particularly the heavy rare earth elements that are not prevalent in commercial bastnasite deposits. These placers derive from the Idaho batholith. The geology, occurrence, and extent of these deposits are reviewed and the diverse mineral assemblages and complex mineral chemical compositions of these sands are described. Niobium, yttrium and thorium are also present in significant concentrations. The results of prior mining practice, including concentration and separation of the heavy minerals are reviewed. Technical approaches to extraction of rare earths from Idaho black sand concentrates are discussed.

Jan 1, 1992

By James O'Brien, Lyman Frost, Grant Hawkes, S. Elangovan, Manohar Sohal, J. S. Herring, Joseph Hartvigsen, Carl Stoots

"Pressing environmental and energy security concerns have brought much needed attention to economic production of hydrogen as the secondary energy carrier for non-electrical markets as well as to meet increasing demand for crude upgrading and desulfurization. While steam reforming of natural gas is currently the dominant method of hydrogen production, it is depleting a valuable fossil fuel while emitting green house gases. Thus, in the long run, efficient, environmentally friendly, and economic means of hydrogen production using nuclear and renewable energy needs to be developed. High temperature electrolysis using solid oxide electrolyte cells is an exceptionally efficient means of generation of high purity hydrogen. It is also capable of directly converting steam and CO2 into synthesis gas. This co-electrolysis process enables conversion of CO2 recovered from concentrated industrial sources into a feedstock for synthetic fuels production. Use of CO2 provides a means of storing hydrogen in a concentrated and convenient form – a hydrocarbon. This is also an effective storage medium for intermittent renewable energy sources such as wind and solar.Ceramatec, Inc and the Idaho National Laboratory are applying solid oxide fuel cell technology to the production of synthesis gas by high temperature co-electrolysis of steam and carbon dioxide. This technology utilizes solid oxide fuel cell stacks to electrochemically remove oxygen from steam and CO2, leaving a clean stream of hydrogen and carbon monoxide suitable for fuel synthesis. By varying the relative concentrations of carbon dioxide and steam, the hydrogen to carbon monoxide product ratio can be controlled as required by the desired type of synthetic fuel being produced from the syngas. The resultant synthesis gas has been used as the feedstock to produce synthetic methane and Fischer Tropsch liquid fuels.Alkaline and proton exchange membrane electrolysis cells typically operate below 100°C, while solid oxide electrolysis cells operates in the 750-850°C range. This higher temperature improves the efficiency significantly. Practically, it translates into a lower cell operating voltage, 1.1-1.4V for high temperature electrolysis vs. ~1.8V for water electrolysis. Hydrogen production is stoichiometric with current in all types of electrolyzers.Carbon dioxide is a valuable resource as a feedstock for energy storage as a hydrocarbon. There is a vast amount of renewable energy that cannot be effectively utilized as grid electricity, but which could be used to convert CO2 to hydrocarbons, offering a solution to the even more difficult (than supplying grid power) challenge of production of sustainable, domestic transportation fuels. Conventional electrolysis and chemical processes could be deployed to accomplish this conversion. However, high temperature co-electrolysis of CO2 and steam to produce synthesis gas using solid oxide fuel cell technology has the potential of improving the efficiency by nearly 50%. A domestic synfuel industry will enable a much larger reliance on intermittent renewable energy than can be accommodated by conventional electric demand profiles while increasing our energy security."

Jan 1, 2010

By Jose Hector Figueroa P.

Mexicana de Cananea, S.A de C.V. is a major copper producer mining a large deposit of the disseminated porphyry type considered one of the largest copper resources of the world with 2.7 billion tons of 0.60% copper for the mill plus 4.1 billion tons of averaging 0.26% copper for leaching. Mining of low grade sulfide leach ore, has been an important part of the overall production of the open pit mine which started in 1944. Before this time all the mining in Cananea was by underground methods. The leaching process in Cananea began on the 1920's with in situ operations in the underground mine and small dumps up to the 1950's. Large scale leaching operations began in 1960 and the copper solutions produced were treated in precipitation plants until 1,980 when the first SX/EW Plant was put in operation in Cananea. Leaching action is essentially ferric-bacterial, with no fiesh acid added to the leaching solutions. Traditionally, 5540% copper extraction is recovered fiom ROM, 70- 120 meter high leach dumps in 80 months of leaching. Cananea has successfully improved copper recoveries by implementing several actions that include: 1. Stripping of old dumps. 2. Leaching of old dumps through slotted casing. 3. Crushing conveying leach ore to minus 8 inch and stacking it in 30 meter lifts. As result of these actions, copper recovery has been increased' to about 70% of total copper with actions 1 and 2 and up to 85% in half the time by crushing-conveying the leach ore, based on the same solubility index of the run-of-mine ore. This paper describes the above actions that were implemented to enhance the leaching recoveries from. sulfide leach dumps and the economics of such actions.

Jan 1, 1999

By W. K. Choi

Stainless steel exposed to wet environments at ambient temperature is subject to the formation of a surface biofilm. Depending upon the prevailing environmental conditions (dissolved oxygen, pH, Eh, concentration of cationic/anionic species), the biofilm may stimulate corrosion through formation of differential aeration zones and concentration cells. Corrosion significantly impacts the United States economy, since on a yearly basis, corrosion induced losses are estimated to be over $200 billion. A large portion of this corrosion is imputable to bacterial activity, and basic information is needed for a better understanding and control of the biocorrosion phenomenon. The present study has investigated the influence of Thiobacillus ferrooxidans in the corrosion of American Iron and Steel Institute (AISI) 304, 316 and 416 stainless steel samples. The formation of biofilm and microstructural changes on the surface of stainless steel samples and their weldments were assessed by microscopic examination, and the changes in the mechanical properties by stress-strain measurements. The significance of the results will be discussed.

Jan 1, 1993

By M. L. Apel

A conceptual approach to the bioremediation of uranium mill tailings (UMT) is presented., This approach focuses on, biosorption to remediate the. effluent solution and bioleaching remediate the. solid fraction. Comparative biosorption studies were performed with synthetic single metal solutions using a commercially available biopolymer. The maximum rate of metal sorption by calcium alginate was found to be 5.43, 6,39, 6.48, and 9.74 mg dm-3 min-1 for U022*, Ba2+, Cd2+ and Zn2+, respectively. Activation energy (AEa) for barium uptake by calcium alginate beads was determined to be 11.5 kJ, indicating a diffusion controlled reaction mechanism. Thermodynamic values (AG+ AH+ and ASt) of the metal-alginate activated complex, as reported in the literature, were found to be in agreement with those calculated from this research. Results show that this biopolymer can be effectively applied in the removal of select metals prevalent in uranium mill tailing effluents and associated waste streams.

Jan 1, 1991

By W. K. Collins

Engineered Scavenger Compounds (ESCs), developed by the U.S. Bureau of Mines, are a novel class of compounds that can selectively recover a desired element from a solid or molten alloy. Lithium titanate (Li2Ti3O7 or L'20-3T'02) is being used as an ESC to recover lithium (Li) from Aluminum-Lithium (Al-Li) alloys. X-ray diffraction measurements have shown that lithium titanate undergoes a phase change from an orthorhombic structure to a hexagonal structure. This change is due to the incorporation of Li in the matrix of the material and the effect of temperature. Although both are metastable, the hexagonal phase that forms during the scavenging of Li from Al-Li alloys appears to be the more stable phase. Recovering Li from the ESC by electrodeposition does not cause the structure to revert to the orthorhombic phase. Both the orthorhombic and the hexagonal structures of Li2Ti3O7 have similar scavenging capacities for Li. This paper proposes a new mechanism for the phase transformation.

Jan 1, 1993

By Dany Racine, Daniel Marceau, Denis Laroche, Dmitry Lukovnikov

Carbon base materials play a critical role in the performance of Hall-Héroult cell. The determination of their thermo-physical properties is of primary importance for modeling and designing complete cell systems. However, overcoming the associated experimental hurdles is complex and often underestimated. Of them are the Poisson’s ratio measurements and the continuous oxidation/burning of the materials at temperatures above 200°C. The novel procedure developed in this research is based on the Gleeble® 3800 system. Its vacuum chamber allows test with a chosen atmosphere at temperature of more than 1000°C. Young’s modulus, Poisson’s ratio and the coefficient of thermal expansion values can all be adequately measured using a single test. Cylindrical carbon samples (: 50mm, L: 100mm) were tested in the modified system at temperatures ranging from room to 950°C without any trace of oxidation. The resulting values were also in good agreement with literature data for a specific graphite material.

Jan 1, 2015

By M. K. Mohan

Lead recovery from process solutions contributes not only to the conservation of resources but also clean environment. Zeolites are natural aluminosilicates, which finds applications as catalysts and in wastewater treatment. In the present investigation, studies were taken up on the processing of Pb from process solutions by zeolites. Effects of pH of the solution, time and type of zeolite viz. chabazite, mordenite, erionite and clinoptilolite on the removal of Pb from solutions was investigated. Rate of sorption was found to depend on the pH of the solution and about 99 pct. recovery was observed at pH 6. Optimal conditions were established for the maximum recovery of lead from process solutions. Possible sorption mechanisms were proposed. The calculated adsorption constants calculated from Langmuir and Freundlich equations showed that the adsorption of lead on chabazite was strong.

Jan 1, 1999

By K. Knuutila

The behaviour of thiourea, animal glue and chloride ions in the electro¬lysis of copper has been investigated by various different electrochemical experiments, i.e. polarization curves with stationary copper electrodes, long-time galvanostatic electrolyses and Hull cell experiments. Polarization curves with stationary copper electrodes show that animal glue has a polarizative effect on the deposition potential. Small thiourea contents affect depolarizatively when high concentrations retard the copper deposition. The microstructures of the deposited copper after the long-time electrolyses show that animal glue favours a basis oriented deposition structure. With thiourea the field orientated structure was evident. It was also observed that the deposited structure depended much on the grain structure of the starter sheet. The chloride ion concentration has a drastic effect on. the crystal size of the deposited copper as it was found out in Hull cell tests. Chloride ions flattened the the crystals and the deposition became smoother when the chloride ions were added. The cathode copper quality is discussed according to the literature. Special attention is paid on the codeposition of thiourea and the origin of sulphur impurities in copper cathodes.

Jan 1, 1987

By Agnes Y. Lee

he U.S. Bureau of Mines developed a method to treat lead-contaminated soil and ebonite battery casing wastes to produce a nonhazardous material. The cleanup procedure involves wet screening to separate a minus 18-mesh soil fraction; removal of metal1ic lead, rocks, wood, etc. ; carbonation to change lead sulfate to acid-soluble lead carbonate; size reduction; acid leaching; and rinsing. The casing wastes undergo size reduction and washing to remove the lead sulfate sludge before carbonation. Similarly, the minus 18-mesh soil is carbonated, then acid leached and rinsed. In leaching, fluosilicic acid (H SiF,) and hydrogen peroxide (H20,) are used to dissolve lead compounds. An electrowinning method is employed to strip lead from the lead-rich leachate. The acid content in the leachate is replenished with fresh H,SiF, acid prior to recycling. Treated casing wastes and soils pass the Toxicity Characteristic Leaching Procedure (TCLP) test and can be reclassified as nonhazardous materia1s. Based on this process, a conceptual pilot plant has been designed which will be demonstrated on wastes from two Superfund sites.

Jan 1, 1993

By L. Lü, M. O. Lai

"Mechanical alloying is a dry, high energy ball milling process which has been used to synthesize metallic powders in the solid state. The present study use this technique to synthesize Cu-base shape memory alloy powder from commercial Cu70Zn30, Cu86Zn14 and element AI powders. The evolution and formation of shape memory alloy powder were monitored using X-ray diffraction and microscopy. It was observed that shape memory alloy powder started to form after 1.8 ks of mechanical alloying. ? phase was clearly detected after 3.6 ks of mechanical alloying. The intensity of X-ray diffraction of the y phase increased when mechanical alloying duration was prolonged indicating an increase in the amount of y phase. Microstructure observation showed different stages of formation of alloyed powders: welding between powders and formation of layered structure, deformation and fracturing of layered structure, and finally the formation of alloyed powders.IntroductionMechanical alloying (MA) is a process used for producing powders with controlled and extremely fine microstructure. It was original developed in 1966 (1) to produce aNi-based superalloy combining oxide dispersion strengthening with gamma prime precipitation hardening. In recent years this technique has been used in producing a wide range of materials including intermetallic compounds (2, 3), amorphous materials (4-6) and other materials (7-9). In MA, a blend of powders is subjected to highly energetic compressive collision. The powder panicles are welded and fractured during ball milling. Therefore, it is essential that at least one of powders should be ductile to act as combiner. It has however been found that brittle components without soft element can also be mechanically alloyed (10), even ceramic powders (11).The present work aims to study the mechanism of formation of shape memory alloy powder during MA."

Jan 1, 1994

By Richard A. Leiby

The recycling of lead-acid batteries in the United States has become a challenge as to how to balance ever increasing environmental regulation and cost with efficient operations. East Penn's captive secondary lead smelter has developed into a recycling facility producing lead, polypropylene, sulfuric acid, ammonium bisulfite, and non-hazardous discard slag. The emphasis has been to design a facility to comply with environmental regulations, to eliminate wastes, and to produce products, while at the same time, continuing to supply the company's battery manufacturing raw material needs.

Jan 1, 1993

By J. R. Hartin

Traditionally, many of the advances in casting technology have been made by expensive and time consuming trial-and-error methodology. Modeling of the complex solidification process promises production of castings which are made "right the first time." Even though several models are available for simulation of conventional casting processes, none of them address this relatively new technology of investment cast titanium aluminides. In this paper, modification and application of a transient, three-dimensional, fully coupled fluid flow and heat transfer solidification modeling computer program to the analysis of centrifugally cast titanium aluminides is discussed. The predictive results of the program are compared to qualities of actual cast parts for validation.

Jan 1, 1992

By A. McLean, S. Dawson, N. D. G. Mountford

"IntroductionIn order to predict the accepted industrial practice for the year 2000, it may be helpful to first consider the rate of development of scientific knowledge. If the speed with which man can travel on commercial vehicles is taken as a criterion for determining the rate of progression, then it can be seen from Figure 1 that advancement in our present century is very rapid. Likewise, if computer technology is used as a criterion for the measurement of scientific advancement, it becomes evident that technological evolution can be highly exponential. These two examples are sufficient to demonstrate that engineers and managers cannot afford to regard scientific development as being linear with respect to time if they are to avoid underestimating the needs of society.Within this framework of overall development, the time required for individual ideas to progress from inception to regular application has decreased considerably. For example, X-rays first discovered by Roentgen in the 1890's and now used widely in medicine and engineering, required a developmental period of some eighty years. The motorcar evolved from early beginnings at the turn of the century to a position of great social impact in sixty years. Rectifier materials used in high frequency radar to the present explosion in communications, required forty years. As illustrated in Figure 2, the period is shortening rapidly.The use of sound waves appears to be following a similar path. There is now a considerable body of knowledge concerning their behaviour and exceptional advances have been made. In medicine and engineering the sonic approach to examination is well established, and acoustic testing forms the basis of several diagnostic and quality control applications. With respect to metals engineering, ultrasonic testing has contributed to the understanding of the relationship between the size and number of internal defects and the probability of premature failure. This has allowed the designer to incorporate appropriate safety factors in his designs; but more importantly, the realization of the deleterious effect of inclusions on the performance of the final product has resulted in a continuous pressure on the material suppliers to reduce the number of defects in their products.It is not only the designer who is demanding defect free material but also the fabricator, as material breakdown during manufacture can be prohibitively expensive. Examples of this can be found in both the aluminum and steel industries where ultra clean sheet is required to ensure that rejections are minimized during beverage can manufacture and other deep drawing operations."

Jan 1, 1988

By F. F. Aplan, G. Simkovich

"A review is given of the effects of solid state point imperfections upon a number of mineral benefication processes and a metal extraction process. It has been found in numerous flotation studies that small amounts of aliovalent impurities (dopants) in binary compounds may show major effects upon flotation behavior. Both semiconducting and ionic conducting compounds are affected. These effects are also seen in hydrometallurgical studies as well as in electrostatic operations. Additionally, de-copperization of lead melts appears to be strongly influenced by similar defects. It is hypothesized that the effects observed in these studies are present in actual operations and should be considered in designing processes. A few speculations concerning future efforts are advanced. IntroductionImperfections [point (e.g., vacancies, interstials, quasi-free electrons, electron holes, impurity ions), line (e.g., dislocations), two dimensional (e.g., grain boundaries) and three dimensional (e.g., 2nd phases) defects] are generally present in solid materials and these imperfections may, and often do, have important effects upon a variety of properties and processes. In general, one may, in most cases, attain elimination of three dimensional defects by a separation process of one type or another (e.g., gravity, electrostatic, magnetic, flotation, hydrometallurgical etc.,). Thus, this type of defect has rarely been investigated in a systematic fashion. Two dimensional defects are always present in non-single crystal materials but have also escaped systematic studies in processes primarily because the control of such defects is not easily attained. Line defects are non-equilibrium entities which are present in ill-defined quantities so that they present a variable that cannot be easily controlled although through careful systematic experiments one can attain some reproducible relations pertaining to this type of defect.Contrary to the lack of studies concerned with the effects of 1, 2 and 3 dimensional types of defects there has been some activity concerned with point defects and their effects upon a number of mineral/metallurgical processes, especially flotation processes. Thus, this article will present a review primarily of point defects in relation to their effects upon flotation although other processes and defects will also be mentioned."

Jan 1, 1988

By Richard D. Hagni

The mineralogy of dusts from the lead sinter and lead blast furnace at the Doe Run Smelter at Herculaneum, Missouri is being studied by reflected light microscopy and scanning electron microscope-energy dispersive spectroscopic analysis (SEM-EDS). Oust from the sinter plant consi5ts of abundant slag and galena particles, and lesser amounts of coke, sinter, and chalcopyrite particles. In contrast, dust from the blast furnace consist of abundant coke and sinter particles, and lesser amounts of slag, galena, chalcopyrite, metallic lead and lead-copper particles. The particles in dusts from remote sampling sites !-l mile from the sinter plant and blast furnace are fine-grained and composed principally of calcium-aluminum silicates that are locally derived, but some of the larger particles consist of sinter, slag, galena, and other minerals. Additional dust samples from the plant and remote sites are currently being studied.

Jan 1, 1991

By Richard J. Abitz

Thennodynamic geochemical models have been applied to assess the relative effectiveness of a variety of reagents added to aqueous waste streams for the removal of radioactive elements. Two aqueous waste streams were examined: effluent derived from the processing of uranium ore and irradiated uranium fuel rods. Simulations of the treatment train were performed to estimate the mass of reagents needed per kilogram of solution, identify pH regions corresponding to solubility minimums, and predict the identity and quantity of precipitated solids. Results generated by the simulations include figures that chart the chemical evolution of the waste stream as reagents are added and summary tables that list mass balances for all reagents and radioactive elements of concern. Model results were used to set initial reagent levels for the treatment trains, minimizing the number of bench-scale tests required to bring the treatment train up to full-scale operation. Additionally, presentation of modeling results at public meetings helps to establish good faith between the federal government, industry, concerned citizens, and media groups.

Jan 1, 1996

By R. Y. Wan, S. L. Chryssoulis

"Gold associations were established in a·biooxidized, chlorinated CIL residue assaying 0.02 oz Ault and in a biooxidized thiosulfate leach residue assaying 0.01 oz Au/t. A detailed mineralogical study involved: assays of screened fractions; light microscopy; ion probe microanalysis to quantify 'invisible' gold in sulfide minerals; proton probe microanalysis to detect and quantify preg-robbed gold. In the CIL residue, most of the gold is preg-robbed (71 %). In the thiosulfate leach residue, gold occurs mainly as submicroscopic disseminations in microcrystalline quartz (chert). In both residues, the 'invisible' gold in pyrite accounts for a minor fraction of the gold assay. Quantitative determination of the gold occurrence in the two residue samples established conclusively that gold adsorption on carbonaceous matter in the thiosulfate leach is of minor importance.Acknowledgement: published with permission of Newmont Gold Company."

Jan 1, 1997